CN104005060A - Electroplating bath - Google Patents
Electroplating bath Download PDFInfo
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- CN104005060A CN104005060A CN201410062671.0A CN201410062671A CN104005060A CN 104005060 A CN104005060 A CN 104005060A CN 201410062671 A CN201410062671 A CN 201410062671A CN 104005060 A CN104005060 A CN 104005060A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
Compositions suitable for the electrodeposition of copper on substrates, such as electronic device substrates, are provided. Methods of depositing copper layers on surfaces and filling apertures with copper are also provided.
Description
Technical field
Relate generally to field of electroplating of the present invention.Particularly, the present invention relates to, on base material, copper is carried out to galvanic deposit.
Background technology
Copper is used to manufacture many electron devices.Plating is a kind of copper to be deposited on to the common method in electronic device substrate, its be usually directed to make electric current in coating solution by two electrodes, one of them electrode is the goods (normally negative electrode) that will carry out plating.The copper (normally copper sulfate) that typical acid copper electroplating solution comprises dissolving, acidic electrolyte bath (its content has electroconductibility in being enough to make bathe), and for improving one or more additives of copper deposition quality.Examples of such additives comprises brightener, flow agent, tensio-active agent and inhibitor.
To thering is the base material of irregular pattern (for example little recess feature), carry out plating and can cause specific difficulty.In electroplating process, along irregular surface, conventionally exist voltage drop to change, this can cause inhomogeneous metal deposition.At voltage drop, change comparatively extreme place, in surperficial obvious irregular situation, the irregular aggravation of plating.As a result of, in this type of surface imperfection, observe thicker metal deposition, be called over-plating.When the plated article of manufacturing such as electron device, the metal level of realizing basic uniform thickness is a very challenging step.In metal deposition is bathed, during particularly copper plating is bathed, conventionally adopt flow agent, so that metal level evenly basic or that flush to be provided on substrate surface.
Along with the contraction of size of electronic devices, electro-deposition of metal layer, for example the purity of copper layer becomes important.In narrow interconnection line, high-caliber impurity can increase the resistivity of metal, and declines because early stage electromigration invalidation makes the probable life of device.Therefore, for metal deposition bath, particularly copper electroplating bath, the trend in industry is the copper deposition that provides purer in narrow interconnection line inside, thereby reduces resistivity the longer electromigration lifetime of promotion of deposition.
Industrial constantly for copper electroplating bath searching additive, for example can provide improved performance, but can not deposit the flow agent that not introduce significantly impurity to resulting copper.Polyethyleneimine: amine is the additive that becomes known for copper electroplating bath.International patent application no WO2011/113908 has disclosed the copper electroplating bath containing alkoxylate poly (alkylenimines) class, the molecular weight of the poly (alkylenimines) main chain of described alkoxylate poly (alkylenimines) class is 300-1,000,000 gram/mol, and replaced by polyalkylene oxide groups, wherein, the average quantity of the oxyalkylene units in described polyalkylene oxide groups is 1.5-10.This patent application points out that the alkoxylate of low degree causes nitrogen content high in additive.Sufficiently high nitrogen content is to cause the reason that well flushes performance on the base material with micron (μ m) or nanometer (nm) size characteristic.But, when this patent points out that nitrogen content is too high in additive, can, in sub-micron features, particularly in Asia-100-nm feature, form defect, for example hole.This patent application points out, the oxyalkylene units that in polyalkylene oxide groups, average quantity is 1.5-10 still shows the good performance that flushes, and can not form extra defect, and particularly diameter is less than or equal to the hole of 100nm.
The present inventor surprisingly finds, nitrogen content can be used in copper electroplating bath higher than the alkoxylate poly (alkylenimines) class of conventional alkoxylate poly (alkylenimines) additive, to provide the copper flushing to deposit and use copper filling pore, the hole of diameter <100nm particularly, it is substantially without the copper of the defect such as hole.
Summary of the invention
The invention provides a kind of copper electroplating bath composition, it comprises: copper ion source; Ionogen; And alkoxylate poly (alkylenimines) additive, described alkoxylate poly (alkylenimines) additive-package is 200-1 containing molecular weight, 000, the poly (alkylenimines) main chain of 000 gram/mol, and nitrogen-atoms is replaced by polyalkylene oxide groups, the average quantity of the oxyalkylene units in described polyalkylene oxide groups is 0.2-1.49.
The present invention also provides a kind of copper has been electroplated to the method on base material, and the method comprises: provide and will carry out with copper the electronic device substrate of plating; Described base material is contacted with composition mentioned above; And apply enough current densities with copper layer on base material.
Accompanying drawing explanation
Fig. 1 and 2 is scanning electron microscope (SEM) photograph (SEM), and it has shown that the aspect ratio that deposits to according to the present invention is the copper in 5 60nm groove.
Embodiment
In whole specification sheets, unless context separately explicitly points out, below abbreviation has following implication: A=ampere; A/dm
2=ampere/square decimeter; MA/cm
2=milliampere(mA)/square centimeter; V=volt; MV=millivolt; ℃=degree Celsius; G=gram; Mg=milligram; Ppm=1,000,000/umber;
nm=nanometer; μ m=micron; Mm=millimeter; Cm=centimetre; DI=deionization; L=liter; And mL=milliliter.Except as otherwise noted, all values are weight percentage, and all ratios are mol ratios.All numerical ranges all comprise end value, can combine mutually with order arbitrarily, just it is apparent that, numerical range sum should be 100%.
In whole specification sheets, " feature " refers to the geometrical shape on base material." hole " refers to recess feature and comprises groove and through hole.In whole specification sheets, term " plating " refers to Metal plating.In this manual, " deposition " and " plating " can exchange use." halogenide " refers to fluorochemical, muriate, bromide and iodide.Except as otherwise noted, term " alkyl " comprises straight chain, branching and cycloalkyl." accelerator " refers to the organic additive of the plating rate that has increased plating bath." inhibitor " refers in electroplating process, suppressed the organic additive of the plating rate of metal." flow agent " refers to can provide substantially the organic compound that flushes (or smooth) metal level.In whole specification sheets, term " flow agent " and " levelling reagent " are used interchangeably.Prefix " one " and " a kind of " represent odd number and plural form.
Plating of the present invention is bathed and method is used in base material, for example, the plated copper layer substantially flushing is provided on semiconductor wafer.Similarly, the present invention can be used for carrying out filling pore with copper, for example, fill silicon perforation (TSV).The compositions and methods of the invention are particularly suitable for copper to be deposited in the hole of diameter <100nm.This type of hole through filling is substantially not contain hole.The hole through filling that term used herein " substantially containing hole " refers to >95% is not containing hole.Preferably >=97% the hole through filling is not contain hole, and more preferably >=98% the hole through filling is not contain hole, and even more preferably the hole through filling is not contain hole.The present invention can be used for copper to be for example deposited on, in the have various aspect ratios hole of (1-10 or larger), and is specially adapted to fill the hole that aspect ratio is 3-8.
The present invention can adopt the copper electroplating bath of wide region.Copper electroplating bath contains copper ion source, ionogen and alkoxylate poly (alkylenimines) additive conventionally, described alkoxylate poly (alkylenimines) additive-package is 200-1 containing molecular weight, 000, the poly (alkylenimines) main chain of 000 gram/mol, and wherein poly (alkylenimines) main chain is replaced by polyalkylene oxide groups, the average quantity of the oxyalkylene units in wherein said polyalkylene oxide groups is 0.2-1.49.Described alkoxylate poly (alkylenimines) has played flow agent in composition of the present invention.Optionally, plating bath can contain one or more various other additives, for example water, accelerator, inhibitor, extra flow agent, source of halide ions, grain refiner, defoamer, alloyed metal and composition thereof.Preferably, copper electroplating bath of the present invention also comprises one or more accelerators, one or more inhibitor and one or more source of halide ions.
In copper electroplating bath, mantoquita is commonly used for copper ion source.Can compatibly adopt any mantoquita dissolving in composition.Exemplary mantoquita includes but not limited to, copper sulfate, sulfonic acid copper, venus crystals, copper gluconate, cupric fluoborate, copper halide, cupric nitrate (II), alkylsulphonic acid copper and aryl sulfonic acid copper.Suitable alkylsulphonic acid copper-clad is drawn together copper methane sulfonate, ethyl sulfonic acid copper and propanesulfonic acid copper.Suitable aryl sulfonic acid copper-clad is drawn together cupric sulfophenate, toluenesulphonic acids copper and sulfocarbolic acid copper.Copper sulfate and alkylsulphonic acid copper are particularly preferred mantoquitas.Also can use the mixture of mantoquita.Described mantoquita is normally commercially available.Can in plating bath of the present invention, use the mantoquita of wider concentration range.Normally, the amount of mantoquita is enough to provide the cupric ion amount of 10-180g/L in plating is bathed.More generally, mantoquita amount provides the cupric ion of 15-70g/L in plating bath.
Ionogen can be alkalescence or acid, normally acid.Can use in the present invention any acid compatible with copper ion source.Suitable acid includes but not limited to: sulfuric acid; Acetic acid; Fluoroboric acid; Nitric acid; Thionamic acid; Phosphoric acid; Haloid acid, example hydrochloric acid; Alkylsulphonic acid and aryl sulfonic acid, as methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, toluenesulphonic acids, sulfocarbolic acid and Phenylsulfonic acid; And halogenated acid, as trifluoromethanesulfonic acid and halogenated acetic acids, as trifluoroacetic acid.Preferably, ionogen is selected from sulfuric acid, alkylsulphonic acid and aryl sulfonic acid.The mixture of acid can be used as ionogen.Conventionally, the amount that ionogen exists is enough to give plating bath electroconductibility.The pH value of acidic electrolyte bath of the present invention is less than 7, is conventionally less than 2.Exemplary alkaline electro plating bath adopts pyrophosphate salt as ionogen, but also can adopt other ionogen.It will be understood by those skilled in the art that if necessary, can regulate by the method for any appropriate electrolytical pH.Described ionogen is normally commercially available, and can directly use or can be further purified.
The total amount that is used for the acidic electrolyte bath of plating bath of the present invention can be 0-200g/L, preferred 5-200g/L, and more preferably 0-120g/L, still also can be used the more acid of high-content for some application, for example, be up to 225g/L, or or even 300g/L.It will be understood by those skilled in the art that by using copper sulfate, alkylsulphonic acid copper or aryl sulfonic acid copper as copper ion source, can be without any extra acid, or use the extra acid of reduction, obtain acidic electrolyte bath.
As a rule, copper electroplating bath also contains water.Water can exist with the amount of wide region.Can use the water of any type, for example distilled water, deionized water or tap water.
Alkoxylate poly (alkylenimines) additive-package for plating bath of the present invention is 200-1 containing molecular weight, 000, the poly (alkylenimines) main chain of 000 gram/mol, and nitrogen-atoms replaced by polyalkylene oxide groups, and the average quantity of the oxyalkylene units in described polyalkylene oxide groups is 0.2-1.49.Preferably, the mean number of the oxyalkylene units in described polyalkylene oxide groups is 0.3-1.45, more preferably 0.3-1.4, more preferably 0.3-1.25, more preferably 0.3-1, even more preferably 0.3-0.75.Term used herein " average quantity of oxyalkylene units " refers to the oxyalkylated degree in poly (alkylenimines), and refers in poly (alkylenimines) main chain, for each N-H group, and the alkoxy base R to polyoxyalkylene unit
1the number that-O averages, for example, numeral be in 1 expression poly (alkylenimines) polymkeric substance for each N-H group, on average have an alkoxy base.
Preferably, alkoxylate poly (alkylenimines) has following formula:
(E
1 2N-R)
a(N(E
1)-R)
b(N(A
1)-R)
c(N(A
2)-R)
dNE
1 2
Wherein, R is C
2-6alkane two bases; A
1it is the continuity of poly (alkylenimines) main chain; A
2be selected from alkyl, thiazolinyl, alkynyl, alkaryl and composition thereof; E
1that chemical formula is-(R
1o)
pr
2polyoxyalkylene unit; Each R
1independently selected from: ethane two bases, 1,2-propane two bases, (2-methylol) ethane two bases, 1,2-butane two bases, 2,3-butane two bases, 2-methyl isophthalic acid, 2-propane two bases, 1-pentane two bases, 1,2-pentane two bases, 2-methyl isophthalic acid, 2-butane two bases, 3-methyl isophthalic acid, 2-butane two bases, 2,3-hexane two bases, 3,4-hexane two bases, 2-methyl isophthalic acid, 2-pentane two bases, 2-ethyl-1,2-butane two bases, 3-methyl isophthalic acid, 2-pentane two bases, 1,2-decane two bases, 4-methyl isophthalic acid, 2-pentane two bases and (2-phenyl) ethane two bases; Each R
2independently selected from: H, alkyl, thiazolinyl, alkynyl, alkaryl and aryl; P is the numeral of 0.2-1.49; A, b, c and d are integers, and a+b+c+d=10 to 24000.Preferably, R is selected from ethane two bases, 1,2-propane two bases and composition thereof.R
2h preferably.Preferably, p=0.3 to 1.45, more preferably 0.3 to 1.4, more preferably 0.3 to 1.25, even more preferably 0.3 to 1, more preferably 0.3 to 0.75.Preferably, d=0.Preferably, a, b and c are respectively the ratios of 1:3 to 3:1, more preferably the ratio of 1:2 to 2:1.Preferably, a+b+c+d=15 to 10000, more preferably 20 to 5000, more preferably 25 to 65 or 1000 to 1800.In poly (alkylenimines) main chain, the average quantity of the oxyalkylene units of each N-H group represents with " p ".
Can be by the poly (alkylenimines) epoxy alkane suitable with one or more be reacted to prepare alkoxylate poly (alkylenimines).Suitable epoxy alkane includes but not limited to, oxyethane, propylene oxide, butylene oxide ring, for example 1,2-butylene oxide ring and 2,3-butylene oxide ring, epoxy pentane and epoxy hexane.Can use the mixture of epoxy alkane.Preferred epoxy alkane comprises oxyethane, propylene oxide, butylene oxide ring and composition thereof, more preferably oxyethane, butylene oxide ring, ethylene oxide/propylene oxide and ethylene oxide/butylene oxide, more preferably ethylene oxide/butylene oxide.Preferred epoxy alkane mixture is to comprise those of oxyethane, for example oxyethane and propylene oxide mixture and oxyethane and butylene oxide ring mixture.When using the mixture of two kinds of epoxy alkane, can use the oxirane of any weight ratio, for example 99:1 to 1:99.The mixture of the epoxy alkane of particularly suitable is that weight ratio is ethyl oxide/oxidation butane of 40:60 to 60:40.In alkoxylate poly (alkylenimines) of the present invention, the ratio of the gross weight of one or more epoxy alkane and the weight of poly (alkylenimines) (weight ratio) conventionally≤2:1, be preferably 0.01:1 to 2:1,0.05:1 to 2:1 more preferably, more preferably 0.05:1 to 1.5:1, more preferably 0.25:1 to 1.5:1.When adopting the epoxy alkane of higher weight ratio: during poly (alkylenimines), in poly (alkylenimines) main chain, the average quantity of the alkoxy base of each N-H group increases.For example,, when operating weight ratio is the epoxy alkane of 5:1: during poly (alkylenimines), in poly (alkylenimines) main chain, the average quantity of the alkoxy base of each N-H group is about 3 or higher a little.
The poly (alkylenimines) of wide region can be used for preparing alkoxylate poly (alkylenimines) of the present invention.This type of poly (alkylenimines) has lower molecular weight conventionally, and 200 grams/mol, preferably 300 grams/mol, more preferably 600 grams/mol.Molecular weight (M
w) the upper limit be generally 1,000,000 gram/mol, preferably 750,000 grams/mol, more preferably 200,000 grams/mol, most preferably 100,000 grams/mol.The scope of the molecular weight of poly (alkylenimines) main chain is preferably 600-10,000 gram/mol.Poly (alkylenimines) is preferably polymine.Suitable poly (alkylenimines) is commercially available, for example, purchased from the BASF AG (BASF (Ludwigshafen, Germany)) of Ludwig, Germany, or can pass through document, and for example in No. 2182306th, United States Patent (USP) prepared by known method.
Can pass through the whole bag of tricks well known in the prior art, for example the method described in international patent application no WO2011/113908 is carried out the alkoxylate of poly (alkylenimines).With epoxy alkane unit, the modification of the N-H unit in poly (alkylenimines) main chain is carried out by the following method: for example, in the situation that existence is up to the water of 80 % by weight, at the temperature of 25-150 ℃, first make polymkeric substance (preferably polyethylene imines) react in the autoclave of agitator is housed with one or more oxiranes.In the first step of reaction, the add-on of epoxy alkane makes the part hydrogen atom of the N-H group of poly (alkylenimines) become hydroxyalkyl, to obtain monoalkoxy poly (alkylenimines).Then from autoclave, remove water.Adding alkaline catalysts, sodium methylate for example, potassium tert.-butoxide, potassium hydroxide, sodium hydroxide, sodium hydride, after potassium hydride KH or base-exchange substance, its add-on is the 0.1-15 % by weight with respect to the adduct obtaining in oxyalkylated first step, to the epoxy alkane that adds additional quantity in the reaction product of first step, thereby obtain alkoxylate poly (alkylenimines), its N-H group for every unit of polymkeric substance contains 0.2-1.49, preferred 0.3-1.45, more preferably 0.3-1.4, more preferably 0.3-1.25, even more preferably 0.3-1, more preferably the epoxy alkane unit of 0.3-0.75.For example at the temperature of 60-150 ℃, carrying out second step.Can in the organic solvent such as dimethylbenzene or toluene, carry out oxyalkylated second step.In order correctly to add epoxy alkane, suggestion, before alkoxylate, is determined the quantity of primary amine group and the secondary amine group of poly (alkylenimines).Or, can carry out by the following method the alkoxylate of poly (alkylenimines): first make poly (alkylenimines) (for example polymine) for example, for example, in suitable solvent (tetrahydrofuran (THF)), react with suitable alkali (potassium hydride KH or sodium hydride), be heated to for example 80 ℃ simultaneously.Then, add required epoxy alkane (epoxide), be further heated to for example be up to 130 ℃.
Optionally, can further in reactions steps, to alkoxylate poly (alkylenimines), carry out functionalized.Further functionalized can plaing a part carries out modification to the character of alkoxylate poly (alkylenimines).For this reason, the mode by the suitable reagent that can react with hydroxyl and/or amino group, transforms the hydroxyl and/or the amino group that in alkoxyalkyl poly (alkylenimines), exist.This has formed functionalized poly-alkoxylation polyene polyamine.Preferably alkoxylate poly (alkylenimines) does not occur further functionalized.Flow agent of the present invention can have any appropriate Polydispersity.Flow agent of the present invention works in the Polydispersity of wide region.
Alkoxylate poly (alkylenimines) can be used for copper electroplating bath of the present invention with the amount of certain limit.As a rule, the concentration≤10mg/L of alkoxylate poly (alkylenimines) amount in composition, concentration is preferably 0.0001-10mg/L, more preferably 0.001-5mg/L, more preferably 0.001-1mg/L.Can use the mixture of alkoxylate poly (alkylenimines).In copper electroplating bath, the total concn of this type of alkoxylate poly (alkylenimines) flow agent mixture is≤1mg/L that concentration is preferably 0.0001-10mg/L, more preferably 0.0001-5mg/L, even more preferably 0.001-5mg/L arbitrarily.
Plating of the present invention is bathed and is preferably contained accelerator.Accelerator (also referred to as brightener) is applicable to the present invention arbitrarily.These accelerators are well known to those skilled in the art.Typical accelerator contains one or more sulphur atoms, and molecular weight is less than or equal to 1000.The accelerator compound with sulfide and/or sulfonic acid group is normally preferred, and concrete compound is to comprise chemical formula R '-S-R-SO
3the group of X, wherein R is the alkyl that can optionally replace, the assorted alkyl that can optionally replace, the aryl that can optionally replace, or the heterocycle that can optionally replace, X is counter ion, for example sodium or potassium, and R ' is hydrogen or chemical bond.Normally, alkyl is C
1-16alkyl, preferably C
3-12alkyl.Assorted alkyl group has one or more heteroatomss, for example nitrogen, sulphur or oxygen conventionally in alkyl chain.Suitable aryl includes but not limited to, phenyl, benzyl, xenyl and naphthyl.Suitable heterocyclic group contains 1-3 heteroatoms conventionally, for example nitrogen, sulphur or oxygen, and 1-3 independently or condensed ring system.This type of heterocyclic group can be aromaticity, or nonaromatic.Preferred accelerator comprises: N, N-dimethyl-dithiocarbamic acid-(3-sulfopropyl) ester; 3-sulfydryl-propanesulfonic acid-(3-sulfopropyl) ester; 3-sulfydryl-propanesulfonic acid sodium salt; Carbonic acid-dithio-o-ethyl ester-s-ester with 3-sulfydryl-1-propanesulfonic acid sylvite; Two-sulfopropyl disulphide; 3-(benzothiazolyl-s-sulfo-) propanesulfonic acid sodium salt; Pyridine propyl group sultaine; 1-sodium-3-sulfydryl propane-1-sulfonate; N, N-dimethyl-dithiocarbamic acid-(3-sulfoethyl) ester; 3-sulfydryl-ethyl propyl sulfonic acid-(3-sulfoethyl) ester; 3-sulfydryl-b sodium salt; Carbonic acid-dithio-o-ethyl ester-s-ester with 3-sulfydryl-1-ethyl sulfonic acid sylvite; Two-sulfoethyl disulphide; 3-(benzothiazolyl-s-sulfo-) b sodium salt; Pyridine ethyl sultaine; And 1-sodium-3-ethane thiol-1-sulfonate.
This type of accelerator can be various consumptions.As a rule, based on bath, the consumption of accelerator is 0.01mg/L(ppm at least), preferred 0.5mg/L at least, more preferably 1mg/L at least.For example, the amount that accelerator exists is 0.01-300mg/L.Those skilled in the art can be according to concrete application, for example, want the pore dimension that will fill on the base material of plating and the density of this type of hole, easily determines the concrete consumption of accelerator.
Any compound that can suppress copper plating rate can be as the inhibitor in plating bath of the present invention.Suitable inhibitor comprises but is not limited to, and polymeric material particularly has heteroatoms and replaces, and more especially has those of oxygen replacement.Exemplary inhibitor is high molecular weight polyether, and for example chemical formula is R-O-(CXYCX ' Y ' O)
nthose of R ', wherein, R and R ' are independently selected from H, C
2-20alkyl and C
6-10aryl; X, Y, X ' and Y ' be respectively independently selected from hydrogen, alkyl, for example methyl, ethyl or propyl group, aryl, for example phenyl or aralkyl, for example benzyl; And n is 5-100,000 integer.Conventionally, one or more X, Y, X ' and Y ' are hydrogen.Preferred inhibitor comprises commercially available polypropylene glycol multipolymer and ethylene glycol copolymer, comprises epoxy ethane-epoxy propane (" EO/PO ") multipolymer and butanols-PEP-101.Suitable butanols-PEP-101 is that weight-average molecular weight is 500-10000, is preferably those of 1000-10000.Other exemplary inhibitor are four functional polyethers that are derived from the addition of different epoxy alkane and quadrol, and are represented by following formula 1 and 2:
Wherein A and B represent different alkylene oxide group parts, and x and y represent respectively the quantity of the repeating unit of each epoxy alkane.Preferably, A and B are selected from C
2-4epoxy alkane, more preferably propylene oxide and oxyethane.Alkoxyl group part in Chemical formula 1 and 2 compound can be block, alternately or random arrangement.Suitable inhibitor material can be bought from many suppliers, for example the commodity of BASF AG (BASF) Pluronic by name and Tetronic.When using this type of inhibitor, the scope of their amount is 1-10000ppm normally, is preferably 5-10000ppm, with the weighing scale of bathing.
Optionally, plating bath of the present invention can contain one or more the second flow agents.Described the second flow agent can be any conventional flow agent.The suitable conventional flow agent that can share with flow agent of the present invention includes but not limited to, United States Patent (USP) the 6th, 610, No. 192 (people such as Step), the 7th, 128, No. 822 (people such as Wang), the 7th, 374, No. 652 (people such as Hayashi), the 6th, 800, No. 188 (people such as Hagiwara), the 8th, 262, No. 895 (people such as Niazimbetova), the 8th, 268, No. 157 (Niazimbetova) and the 8th, those that disclose in 268, No. 158 people such as () Niazimbetova.Preferred the second flow agent comprises the reaction product of imidazoles and epoxide, and for example United States Patent (USP) the 8th, those that disclose in 268, No. 158.The amount of this type of the second flow agent is well known by persons skilled in the art, the gross weight of bathing in plating, and its consumption is generally 0.01-5000ppm, but consumption also can be more or less.Preferably, the total concn of described the second flow agent is 0.25-5000ppm, more preferably 0.25-1000ppm, more preferably 0.25-100ppm.In one embodiment, copper electroplating bath of the present invention does not preferably contain the second flow agent.
Plating bath of the present invention optionally contains halogen ion source, preferably contains halogen ion source.Chlorion is preferred halogen ion.Exemplary chloride-ion source comprises cupric chloride and hydrochloric acid.Can use the halide ion concentration of wide region in the present invention.As a rule, based on plating, bathe, halide ion concentration scope is 0-100ppm, is preferably 10-100ppm.Preferred halide ion concentration is 20-75ppm.This type of halogen ion source is normally commercially available, and can be without being further purified use.
In copper electroplating bath, optionally there are one or more alloyed metal sources.Exemplary alloy metal includes but not limited to, tin, zinc, indium, antimony and bismuth etc.Form with the bath soluble of any appropriate joins this type of alloyed metal in plating bath.For example, thereby can be used for copper electroplating bath of the present invention can deposited copper or copper alloy, tin-copper and tin-copper-bismuth.The amount in this type of alloyed metal source in plating bath depends on selected special metal and the particular alloy that will deposit.Described amount is well known to those skilled in the art.
Plating bath of the present invention is water-based normally.Except as otherwise noted, all concentration of component are in water-based system.Specially suitable composition as plating bath of the present invention comprises soluble copper salt, acidic electrolyte bath, accelerator, inhibitor, halogen ion and the alkoxylate poly (alkylenimines) as flow agent mentioned above.More preferably, suitable composition comprises that the soluble copper salt of 10-220g/L is as copper metal, the acidic electrolyte bath of 5-250g/L, the accelerator of 1-50mg/L, the inhibitor of 1-10000ppm, the halogen ion of 10-100ppm, the alkoxylate poly (alkylenimines) mentioned above of 0.0001-1mg/L, the second flow agent of optional 0.01-5000ppm, surplus is water, to obtain 1L.
Can be by preparing plating bath of the present invention with random order in conjunction with component.Preferably, first by inorganic component, for example copper ion source, water, ionogen and optional halogen ion source join in plating bath container, add afterwards organic constituent, for example flow agent, accelerator, inhibitor and any other organic constituent.
Plating of the present invention is bathed and can at the temperature of any appropriate, be used, for example 10-65 ℃ or higher.Preferably, the temperature that plating is bathed is 10-35 ℃, more preferably 15-30 ℃.
Conventionally, copper electroplating bath of the present invention stirs during use.The present invention can use the stirring means of any appropriate, and these class methods are well-known in the art.Suitable stirring means includes but not limited to, air spray, workpiece stirring and impact.When copper electroplating bath of the present invention is during for the base material of plating such as semiconductor wafer, wafer can be rotated with suitable speed, for example 1-1000rpm, preferably 1-250rpm, more preferably 200rpm, and by pumping or injection, plating bath composition is contacted with the wafer of rotation.Or wafer is without selection, but the mobile metal that is enough to provide required that plating is bathed deposits.
Term used herein " semiconductor wafer " is intended to comprise " electronic device substrate ", " semiconductor substrate ", " semiconducter device " and for the various encapsulation of various interconnect level, comprises encapsulation or other assemblies that need to be welded to connect of single-wafer, multi-disc wafer, various levels.Specially suitable base material is patterned wafers, for example patterned silicon wafer, patterning sapphire wafer and patterning gallium-arsenic wafer.This type of wafer can be the size of any appropriate.Preferred wafer diameter is 200-300mm, but has less or larger-diameter wafer also applicable to the present invention.Term used herein " semiconductor substrate " comprises any base material with one or more layers semiconductor layer or structure, and it comprises the movable of semiconducter device or can function part.Term " semiconductor substrate " is defined as the arbitrary structures that expression comprises semiconductor material, include but not limited to, bulk semiconductor material, for example, semiconductor wafer in single semiconductor wafer or contain the semiconductor wafer in the assembly of other materials on it, and independent semiconductor material layer or the assembly that comprises other materials.Semiconducter device refers on it manufactures the semiconductor substrate that has or carrying out manufacturing in batches at least one microelectronic device in batches.
By base material and metal deposition of the present invention bathe contact and apply for some time current density so that layer metal deposition to base material, base material is electroplated.Base material is usually used as negative electrode.Plating is bathed and is contained anode, and it can be solubility or insoluble.Conventionally to negative electrode, apply electromotive force.Apply sufficient current density and carry out the plating of for some time, this time is enough to the metal level that on base material deposition has desired thickness, for example copper layer.For plated copper on electron device, suitable current density includes but not limited to, 1-250mA/cm
2scope.Normally, when the present invention is for when unicircuit is manufactured deposited copper, current density range is 1-75mA/cm
2.Depend on the special metal that will deposit and want the specific base material of plating, the crosslinking polymerization flow agent of selection and well known by persons skilled in the art other are considered, can use other current densities.The selection of described current density is well known by persons skilled in the art.
An advantage of the present invention is to have reduced over-plating, particularly piles up (mounding).The described over-plating that reduced means during subsequent chemical-mechanical polishing process, during particularly semi-conductor is manufactured, for example, for removing the time that metal (copper) spends and making great efforts less.Another advantage of the present invention is, can in single base material, fill the pore dimension of wide region, the groove that particularly through hole of diameter <100nm and width are 100nm.Thereby the present invention is specially adapted to fill significantly the hole of the various size in base material, for example groove and perforation (comprising TSV), it has respectively the size (diameter or width) of <100nm.According to the present invention, with the hole that copper is filled, can there are various aspect ratios, for example, be more than or equal to 10, be specially 3-8.
Electron device such as semiconducter device, semiconductor packages and printed circuit board (PCB) formed according to the present invention, the feature through filling that it has the copper layer of substantially flat and does not substantially contain additional defects.The copper layer of " substantially flat " refers to terrace land height, and intensive very little pore region is less than 1 μ m with the difference that does not contain or substantially do not contain the region of hole, is preferably less than 0.75 μ m, is more preferably less than 0.6 μ m, is even more preferably less than 0.1 μ m." substantially not containing extra defect " refers to than the contrast plating that does not contain flow agent and bathes, and described flow agent can not increase the defect in the hole through filling, for example quantity in hole or size.Another advantage of flow agent of the present invention is, can on the base material of hole with non-homogeneous size, deposit the metal level of substantially flat, and wherein, described hole is not substantially containing extra hole." hole of non-homogeneous size " refers to the hole in same substrate with various size.
A special advantage of plating bath of the present invention is, is being up to initially
or or even be up to initial
copper deposition in, in copper layer, almost do not observe mixing of impurity.This has realized in the dual damascene technique of manufacturing for unicircuit, with very pure copper, deposits filling vias (" gap-fill ").Especially, the invention provides the copper deposition in the hole of filling at copper for example, its have carbon, nitrogen, halogenide, oxygen and sulphur in deposition average≤total impurities of 150ppm.
Although method of the present invention has been carried out to general description with reference to semi-conductor manufacture, it should be understood that, the present invention can be used for substantially flushing or smooth copper deposition and needs do not contain any electrolysis process of the metal filled feature in hole substantially.This type of technique comprises printed circuit board (PCB) and unicircuit manufacture.For example, plating of the present invention is bathed and be can be used for the through hole on printed circuit board (PCB), pad or trace (trace) to carry out plating, and for wafer is carried out to projection plating.Other suitable techniques comprise encapsulation and interconnection manufacture, and wherein suitable base material comprises lead frame and interconnection.
embodiment 1: general step.in pressure reactor, prepare oxyalkylated polymine (PEI).To the aqueous solution that adds PEI initiator (3mL, 50 % by weight) in glass bushing pipe, then by under reduced pressure, 80 ℃ of dry making a return journey for 10 hours, dewater.On experiment same day, to the mixture that adds potassium hydride KH (16mg) and tetrahydrofuran (THF) (2mL) in each bushing pipe.Bushing pipe is loaded in pressure reactor, and is heated to 80 ℃.Then in a shot, add 1 of concrete amount, 2-butylene oxide ring (BO), and be heated to 130 ℃.Once judge and consume the BO that is over by the stabilization of reactor pressure, add the oxyethane (EO) of specified quantitative.Once consume the EO that is over, reactor cooling is also ventilated.H with 1M
2sO
4sudden cold residual catalyst, and under reduced pressure remove volatile matter.
According to the alkoxylate polymine in above-mentioned steps preparation table 1." PEI Mw " refers to the weight-average molecular weight of initial polymine, and unit is dalton." weight ratio " refers to the total amount of epoxide and the weight ratio of PEI." epoxide " refers to used concrete epoxide (BO=butylene oxide ring, EO=oxyethane); " mol ratio " refers in PEI main chain total mole of epoxide of the N-H group of every mole.
Table 1
embodiment 2:by mixing the CuSO of 60g/L
4, 50g/L the H of 18N
2sO
4, the chlorion (HCl as chloride-ion source) of 50ppm, the di-sulphide compounds of 8mL/L prepare copper electroplating bath as four copolymers containing hydroxyl and carboxyl groups of accelerator, 7.5mL/L as the flow agent compound of the embodiment 1 of inhibitor and 0.5mg/L, described di-sulphide compounds has sulfonic acid group and molecular weight <1000, described four copolymers containing hydroxyl and carboxyl groups are derived from the addition of oxyethane and propylene oxide and quadrol, the molecular weight of described four copolymers containing hydroxyl and carboxyl groups is about 7500, and the ratio of EO/PO is 1.8.At 25 ℃, use Parstat
tM2273 pressurestats carry out cyclic voltammetry measurement.Area is 0.126cm
2rotation (1000rpm) platinum disk electrode as working electrode, there is the H of 10 volume %
2sO
4ag/AgCl bridge as reference, platinum filament is as to electrode.Before each measurement, electrode is being cleaned, described measurement by-0.2V between+1.6V, at the H of 10 volume %
2sO
4in loop.Scanning speed with 50mV/s is carried out electrochemical measurement.Between-0.2V to 1.6V, carry out complete cycle four times, storage is circulation for the last time, and uses PowerSuite
tMsoftware is analyzed.Table 2 recorded data shows the flow agent sample of embodiment 1, and has summed up at 40mA/cm
2corresponding electrochemical polarization, and under high-quality transmission condition (1000rpm), the integral charge obtaining from its cyclic voltammetric stripping peak (stripping peak).In table 2, E=40mA/cm
2polarization, unit is millivolt (mV), electric charge refers to from the quantity of electric charge of electrode stripping, unit is millicoulomb (mC), to obtain in the given measurement of how much copper that imposed a condition lower plating.
Table 2
| Flow agent sample number into spectrum | E(mV) | Electric charge (mC) |
| 1 | -121.99 | -24.68 |
| 2 | -104.31 | -28.9 |
| 3 | -72.42 | -40.03 |
| 4 | -63.13 | -43.62 |
| 5 | -60.12 | -44.65 |
| 6 | -63.51 | -44.87 |
| ? | ? | ? |
| Comparative example 1 | -43.27 | -50.24 |
| Comparative example 2 | -46.48 | -51.5 |
| Comparative example 3 | -35.06 | -57.59 |
Data presentation flow agent sample of the present invention in table 2 has respectively rejection characteristic, shows that sample has played respectively flow agent in copper electroplating bath.Electric charge absolute value in table 2 is as the index of relative inhibition (or levelling) intensity of sample, and less electric charge shows to have less copper, thereby sample has stronger inhibition strength (or levelling ability) than having compared with the sample of large charge absolute value.As can be seen from these data, than the conventional alkoxylate poly (alkylenimines) of mean number >=1.5 of oxyalkylene units in polyoxyalkylene, flow agent compound of the present invention has obviously stronger rejection characteristic.
embodiment 3:by mixing the CuSO of 40g/L
4, 30g/L the H of 18N
2sO
4, the chlorion of 50ppm (HCl is as chloride-ion source), the di-sulphide compounds of 6-8mL/L is as accelerator, four copolymers containing hydroxyl and carboxyl groups of 8-10mL/L are as inhibitor, the flow agent compound of the embodiment 1 of 0.5-1.5mg/L and the second flow agent of 5-10mg/L, prepare copper electroplating bath, described di-sulphide compounds has sulfonic acid group and molecular weight <1000, described four copolymers containing hydroxyl and carboxyl groups are derived from the addition of oxyethane and propylene oxide and quadrol, the molecular weight of described four copolymers containing hydroxyl and carboxyl groups is about 7500, and the ratio of EO/PO is 1.8, described the second flow agent is 4-phenylimidazole, 2, 4-methylimidazole and 1, the reaction product of 4-bis-(oxyethane-2-yl) butane.
In wafer section plating (WSP) instrument, carry out the experiment of copper plating, to simulate actual plating tool.Patterned wafers sample (4cm x4cm) is connected on the cylindrical tetrafluoroethylene head with the rotating electrode (pine instrument (Pine Instruments)) that fixedly conducting metal presss from both sides.Speed setting is 200rpm, uses commercially available testing wafer, Q-Cleave D(QCD) or 454 wafers carry out electrostatic precipitation.These testing wafers take on a different character respectively.For example, QCD wafer is containing fluted row section and pad (pad) (or square (square) or box (box)), and 454 wafers contain pattern structure.For QCD wafer plating, in following steps, deposited the copper film of 1 μ m: 7mA/cm
2under
10mA/cm
2under
and 40mA/cm
2under
for 454 wafer plating, at 7mA/cm
2under deposited
copper film.Hot entry condition is set as 0.3V and 200rpm.
Use the QCD sample wafer of Lycra opticmicroscope assessment copper plating (thickness is 1 μ m), to determine whether to exist surface imperfection.Under 5 times of magnifications, detect box, under 10 times of magnifications, detecting groove row section, flushes with characterization of surfaces.Box does not demonstrate for example surface imperfection of tubercle and so on, and groove row section does not demonstrate visible columns.When not seeing row in groove row section, it is effective flow agent that the flow agent sample that used is electroplated for copper.
For 454 samples, capture the cross section scanning electron microscope (SEM) photograph (SEM) under 50,000 magnifications, take and monitor the gap-fill in damascene feature (groove of the 60nm that aspect ratio is 5).Sample demonstrates excellent gap-fill (copper is deposited in groove), without hole, forms.Fig. 1 is the SEM figure showing containing the copper electroplating bath clearance filling capability of flow agent of the present invention, and wherein copper plating is bathed the accelerator that contains 8mL/L, the flow agent sample 2 of the inhibitor of 6mL/L and 0.5ppm.
embodiment 4:repeat the process of embodiment 1, difference is to replace butylene oxide ring with propylene oxide (PO), so that the poly (alkylenimines) of the alkoxylate in table 3 to be provided.Then according to embodiment 2, prepare copper electroplating bath, difference is that the alkoxylate poly (alkylenimines) in table 3 is used as flow agent.According to embodiment 2, carry out cyclic voltammetry, the results are shown in Table 3.
Table 3
Data presentation flow agent sample of the present invention (sample 7-12) in table 3 has respectively rejection characteristic, shows that sample has played respectively flow agent in copper electroplating bath.As can be seen from these data, the conventional alkoxylate poly (alkylenimines) that is 1.5-10 than the mean number of the oxyalkylene units in polyalkylene oxide groups, flow agent compound of the present invention has obviously stronger rejection characteristic.Specifically, in PEI main chain, to have the electric charge of the comparative example 4 that is on average about 3 epoxy alkane be-47.68 to each N-H group, and the electric charge that in PEI main chain, each N-H group has a sample of the present invention 7 that is on average about 0.3 epoxy alkane part is-27.24, show that the inhibition strength of sample 7 is apparently higher than comparative example 4.
embodiment 5:the general process that repeats embodiment 1, difference is only to use single epoxide, and oxyethane (EO) or propylene oxide (PO), to provide the poly (alkylenimines) of the alkoxylate in table 4.Then according to embodiment 2, prepare copper electroplating bath, difference is that the alkoxylate poly (alkylenimines) in table 4 is used as flow agent.According to embodiment 2, carry out cyclic voltammetry, the results are shown in Table 4.
Table 4
Data presentation flow agent sample of the present invention (sample 13-23) in table 4 has respectively rejection characteristic, shows that sample has played respectively flow agent in copper electroplating bath.As can be seen from these data, than the conventional alkoxylate poly (alkylenimines) of mean number >=1.5 of oxyalkylene units in polyalkylene oxide groups, flow agent compound of the present invention has obviously stronger rejection characteristic.Specifically, in PEI main chain, to have the electric charge of the comparative example 7 that is on average about 3 epoxy alkane be-51.88 to each N-H group, and the electric charge that in PEI main chain, each N-H group has a sample of the present invention 13 that is on average about 0.3 epoxy alkane is-25.29, shows that the inhibition strength of sample 13 is apparently higher than comparative example 7.
embodiment 6:with the plating of embodiment 3, bathe at the upper plated copper layer of 454 sample wafer samples (4cm x4cm), the plating of described embodiment 3 is bathed the accelerator that contains 8mL/L, the inhibitor of 6mL/L and the sample of 0.6mg/L 7 are as flow agent, with the flight time, SIMS assesses it, to determine the mean level (ML) of impurity in copper film.Find that average impurity level is 117ppm.
embodiment 7:use containing the copper plating of different flow agents and bathe the process that repeats embodiment 6.Copper plating bath A(contrast) the commercially available henzylate polymine that contains 0.75mg/L is as the 4-phenylimidazole, 2 of the first flow agent and 5mg/L, the reaction product of 4-methylimidazole and Isosorbide-5-Nitrae-bis-(oxyethane-2-yl) butane is as the second flow agent.The sample 2 that copper plating bath B contains 0.75mg/L is as the 4-phenylimidazole, 2 of the first flow agent and 5mg/L, and the reaction product of 4-methylimidazole and Isosorbide-5-Nitrae-bis-(oxyethane-2-yl) butane is as the second flow agent.The results are shown in Table 5, show that flow agent of the present invention has the impurity combination of obvious reduction in copper film.
Table 5
embodiment 8:by mixing the CuSO of 40g/L
4, 30g/L the H of 18N
2sO
4, the chlorion (HCl as chloride-ion source) of 50ppm, the di-sulphide compounds of 8mL/L prepare copper electroplating bath as the sample 13 of the embodiment 5 of inhibitor and 0.5mg/L as flow agent compound as four copolymers containing hydroxyl and carboxyl groups of accelerator, 5mL/L, described di-sulphide compounds has sulfonic acid group and molecular weight <1000, described four copolymers containing hydroxyl and carboxyl groups are derived from the addition of oxyethane and propylene oxide and quadrol, the molecular weight of described four copolymers containing hydroxyl and carboxyl groups is about 7500, and the ratio of EO/PO is 1.8.According to the step described in embodiment 3, testing the upper plated copper layer of 454 wafer design samples (4cm x4cm).For 454 samples, capture the cross section scanning electron microscope (SEM) photograph (SEM) under 50,000 magnifications, demonstrate good gap-fill (copper is deposited in the groove that aspect ratio is 5 60nm), without hole, form.
Claims (15)
1. a composition, it comprises: copper ion source; Ionogen; And alkoxylate poly (alkylenimines) additive, described alkoxylate poly (alkylenimines) additive-package is 200-1 containing molecular weight, 000, the poly (alkylenimines) main chain of 000 gram/mol, and nitrogen-atoms is replaced by polyalkylene oxide groups, the average quantity of the oxyalkylene units in described polyalkylene oxide groups is 0.2-1.49.
2. composition as claimed in claim 1, is characterized in that, the average quantity of the oxyalkylene units in described polyalkylene oxide groups is 0.3-1.45.
3. composition as claimed in claim 1, is characterized in that, described polyalkylene oxide groups comprises ethylene oxide unit, propylene oxide units, epoxybutane unit and composition thereof.
4. composition as claimed in claim 1, is characterized in that, described polyalkylene oxide groups comprises the mixture of ethylene oxide unit and epoxybutane unit.
5. composition as claimed in claim 4, is characterized in that, the ratio of described oxyethane and butylene oxide ring is 1:9 to 9:1.
6. composition as claimed in claim 1, is characterized in that, described alkoxylate poly (alkylenimines) has chemical formula: (E
1 2n-R)
a(N (E
1)-R)
b(N (A
1)-R)
c(N (A
2)-R)
dnE
1 2; Wherein, R is C
2-6alkane two bases; A
1it is the continuity of poly (alkylenimines) main chain; A
2be selected from alkyl, thiazolinyl, alkynyl, alkaryl and composition thereof; E
1that chemical formula is-(R
1o)
pr
2polyoxyalkylene unit; Each R
1independently selected from: ethane two bases, 1,2-propane two bases, (2-methylol) ethane two bases, 1,2-butane two bases, 2,3-butane two bases, 2-methyl isophthalic acid, 2-propane two bases, 1-pentane two bases, 1,2-pentane two bases, 2-methyl isophthalic acid, 2-butane two bases, 3-methyl isophthalic acid, 2-butane two bases, 2,3-hexane two bases, 3,4-hexane two bases, 2-methyl isophthalic acid, 2-pentane two bases, 2-ethyl-1,2-butane two bases, 3-methyl isophthalic acid, 2-pentane two bases, 1,2-decane two bases, 4-methyl isophthalic acid, 2-pentane two bases and (2-phenyl) ethane two bases; Each R
2independently selected from: H, alkyl, thiazolinyl, alkynyl, alkaryl and aryl; P is 0.2 to 1.49 numeral; A, b, c and d are integers, and a+b+c+d=10 to 24000.
7. composition as claimed in claim 6, is characterized in that, R is selected from ethane two bases, 1,2-propane two bases and composition thereof.
8. composition as claimed in claim 6, is characterized in that, R
2h.
9. composition as claimed in claim 6, is characterized in that p=0.3 to 1.45.
10. composition as claimed in claim 6, is characterized in that, d=0.
11. compositions as claimed in claim 1, said composition also comprises one or more accelerators, inhibitor, flow agent, halogen ion, defoamer and alloyed metal ion source.
12. compositions as claimed in claim 1, is characterized in that, concentration≤1ppm that in described composition, alkoxylate poly (alkylenimines) exists.
13. compositions as claimed in claim 12, is characterized in that, the concentration that in described composition, alkoxylate poly (alkylenimines) exists is 0.0001-1ppm.
The method of 14. 1 kinds of acid copper, described method comprises: provide and will carry out with copper the electronic device substrate of plating; Described base material is contacted with composition claimed in claim 1; And apply enough current densities with copper layer on base material.
15. methods as claimed in claim 14, is characterized in that, the hole that described electronic device substrate comprises size≤100nm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/776,692 US20140238868A1 (en) | 2013-02-25 | 2013-02-25 | Electroplating bath |
| US13/776,692 | 2013-02-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104005060A true CN104005060A (en) | 2014-08-27 |
Family
ID=50073067
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410062671.0A Pending CN104005060A (en) | 2013-02-25 | 2014-02-24 | Electroplating bath |
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|---|---|
| US (1) | US20140238868A1 (en) |
| EP (1) | EP2770087A1 (en) |
| JP (1) | JP2014162995A (en) |
| KR (1) | KR20140106426A (en) |
| CN (1) | CN104005060A (en) |
| TW (1) | TW201439211A (en) |
Cited By (5)
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| CN106086954A (en) * | 2015-04-27 | 2016-11-09 | 罗门哈斯电子材料有限责任公司 | Acid copper electroplating bath and the method being used for electroplating the copper deposit of low internal stress and good malleability |
| CN107602842A (en) * | 2017-08-21 | 2018-01-19 | 沈阳浩博实业有限公司 | A kind of branched structure polyether antifoam agent and preparation method thereof |
| CN110424030A (en) * | 2019-08-30 | 2019-11-08 | 广州三孚新材料科技股份有限公司 | Cyanide-free alkaline copper electroplating solution, preparation thereof and application thereof in flexible printed circuit board |
| CN110741109A (en) * | 2017-06-16 | 2020-01-31 | 安美特德国有限公司 | Aqueous acidic copper electroplating bath and method for electrolytically depositing copper coatings |
| CN113604845A (en) * | 2021-08-27 | 2021-11-05 | 安徽华威铜箔科技有限公司 | Preparation method of electrolytic copper foil additive for 3.5-micron power lithium battery, product and application of product |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI710671B (en) | 2014-09-15 | 2020-11-21 | 美商麥德美樂思公司 | Levelers for copper deposition in microelectronics |
| EP3344800B1 (en) * | 2015-08-31 | 2019-03-13 | ATOTECH Deutschland GmbH | Aqueous copper plating baths and a method for deposition of copper or copper alloy onto a substrate |
| US9922874B2 (en) * | 2016-07-01 | 2018-03-20 | Applied Materials, Inc. | Methods of enhancing polymer adhesion to copper |
| CN109952390A (en) * | 2016-09-22 | 2019-06-28 | 麦克德米德乐思公司 | The electro-deposition of copper in microelectronics part |
| BR112019015180B1 (en) * | 2017-02-13 | 2023-11-07 | Basf Se | PROCESS FOR MANUFACTURING AN ALKOXYLATED POLYALKYLENEIMINE, AND ALKOXYLATED POLYALKYLENEIMINE |
| PT3483307T (en) * | 2017-11-09 | 2020-07-03 | Atotech Deutschland Gmbh | Plating compositions for electrolytic copper deposition, its use and a method for electrolytically depositing a copper or copper alloy layer onto at least one surface of a substrate |
| WO2021058336A1 (en) * | 2019-09-27 | 2021-04-01 | Basf Se | Composition for copper bump electrodeposition comprising a leveling agent |
| EP4034696A1 (en) * | 2019-09-27 | 2022-08-03 | Basf Se | Composition for copper bump electrodeposition comprising a leveling agent |
| KR20220124787A (en) * | 2020-01-10 | 2022-09-14 | 램 리써치 코포레이션 | Improved TSV process window and fill performance by long pulsing and ramping |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1069211A2 (en) * | 1999-07-15 | 2001-01-17 | The Boc Group, Inc. | Electroplating solutions |
| CN1865516A (en) * | 2005-04-28 | 2006-11-22 | 台湾积体电路制造股份有限公司 | Electroplating solution and electroplating method |
| WO2011113098A1 (en) * | 2010-03-17 | 2011-09-22 | Innovative Design Technology Pty Limited | A centrifugal compressor |
| US20120097547A1 (en) * | 2010-10-25 | 2012-04-26 | Universiteit Gent | Method for Copper Electrodeposition |
| CN102888629A (en) * | 2010-03-15 | 2013-01-23 | 罗门哈斯电子材料有限公司 | Copper electroplating bath and method |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2182306A (en) | 1935-05-10 | 1939-12-05 | Ig Farbenindustrie Ag | Polymerization of ethylene imines |
| US4036711A (en) * | 1975-12-18 | 1977-07-19 | M & T Chemicals Inc. | Electrodeposition of copper |
| CA1105045A (en) * | 1977-05-04 | 1981-07-14 | Hans G. Creutz (Deceased) | Electrodeposition of copper |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US5174886A (en) * | 1991-02-22 | 1992-12-29 | Mcgean-Rohco, Inc. | High-throw acid copper plating using inert electrolyte |
| US6610192B1 (en) | 2000-11-02 | 2003-08-26 | Shipley Company, L.L.C. | Copper electroplating |
| WO2002090623A1 (en) | 2001-05-09 | 2002-11-14 | Ebara-Udylite Co., Ltd. | Copper plating bath and method for plating substrate by using the same |
| US7316772B2 (en) * | 2002-03-05 | 2008-01-08 | Enthone Inc. | Defect reduction in electrodeposited copper for semiconductor applications |
| US20060191798A1 (en) * | 2003-04-03 | 2006-08-31 | Fukuda Metal Foil & Powder Co., Ltd. | Electrolytic copper foil with low roughness surface and process for producing the same |
| JP2004346422A (en) * | 2003-05-23 | 2004-12-09 | Rohm & Haas Electronic Materials Llc | Plating method |
| US7128822B2 (en) | 2003-06-04 | 2006-10-31 | Shipley Company, L.L.C. | Leveler compounds |
| TW200632147A (en) * | 2004-11-12 | 2006-09-16 | ||
| EP1741804B1 (en) | 2005-07-08 | 2016-04-27 | Rohm and Haas Electronic Materials, L.L.C. | Electrolytic copper plating method |
| US8268157B2 (en) | 2010-03-15 | 2012-09-18 | Rohm And Haas Electronic Materials Llc | Plating bath and method |
| US8262895B2 (en) | 2010-03-15 | 2012-09-11 | Rohm And Haas Electronic Materials Llc | Plating bath and method |
| MY156690A (en) * | 2010-03-18 | 2016-03-15 | Basf Se | Composition for metal electroplating comprising leveling agent |
| JP5595301B2 (en) * | 2011-02-22 | 2014-09-24 | Ｊｘ日鉱日石金属株式会社 | Copper electrolyte |
-
2013
- 2013-02-25 US US13/776,692 patent/US20140238868A1/en not_active Abandoned
-
2014
- 2014-02-13 EP EP14155052.5A patent/EP2770087A1/en not_active Withdrawn
- 2014-02-19 JP JP2014029493A patent/JP2014162995A/en active Pending
- 2014-02-21 TW TW103105792A patent/TW201439211A/en unknown
- 2014-02-24 CN CN201410062671.0A patent/CN104005060A/en active Pending
- 2014-02-24 KR KR1020140021216A patent/KR20140106426A/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1069211A2 (en) * | 1999-07-15 | 2001-01-17 | The Boc Group, Inc. | Electroplating solutions |
| CN1865516A (en) * | 2005-04-28 | 2006-11-22 | 台湾积体电路制造股份有限公司 | Electroplating solution and electroplating method |
| CN102888629A (en) * | 2010-03-15 | 2013-01-23 | 罗门哈斯电子材料有限公司 | Copper electroplating bath and method |
| WO2011113098A1 (en) * | 2010-03-17 | 2011-09-22 | Innovative Design Technology Pty Limited | A centrifugal compressor |
| US20120097547A1 (en) * | 2010-10-25 | 2012-04-26 | Universiteit Gent | Method for Copper Electrodeposition |
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| CN106086954A (en) * | 2015-04-27 | 2016-11-09 | 罗门哈斯电子材料有限责任公司 | Acid copper electroplating bath and the method being used for electroplating the copper deposit of low internal stress and good malleability |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20140238868A1 (en) | 2014-08-28 |
| JP2014162995A (en) | 2014-09-08 |
| KR20140106426A (en) | 2014-09-03 |
| EP2770087A1 (en) | 2014-08-27 |
| TW201439211A (en) | 2014-10-16 |
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